Azo dyes.



UNITED STATES PATENT OFFICE.

WILHELM NEELMEIER AND AUGUST SIG'WART, OF LEVEBKUSEN, NEAR COLOGNE, GERMANY, ASSIGNORS TO SYNTHETIC PATENTS CO., INC., 01? NEW YORK, N. Y.. A

CORPORATION OF NEW YORK.

Patented Feb. 16, 1915.

AZO DYES.

1 ,128,813, Specification of Letters Patent.

No Drawing.

To all whom it may concern Be it known that weflVrLnnLM NEELMEIER and AUuUsr Srowaar, doctors of philosophy, chemists, citizens of the German Empire, residing at Leverkusen, near Cologneonthe-Rhine, Germany, have invented new and useful Improvements in New Azo Dyes. of which the following is a specification.

We have found that new and valuable azo dye-stuffs can be obtained on starting from a derivative of the 2-naphthol-(S-sulfonic of 4-ehloro-2-aminophenol-G-sulfonic acid Oli The above mentioned hitherto unknown derivatives of the 2-naphthol-ti-sulfonic acid can be obtained by condensing the sulfonylchlorid of the Q-naphthol-l-carboxylic acid with phenols, ammonia, amins, aminosalicylic acid, etc., and splitting oil the carboxylic group. 1n case the products which still contain this group are coupled the carboxylic group is eliminated in the process of combination. These compounds can be combined with one molecule of a diazo compound, diazoazo compound or two molecules with a tetrazo compound, or an intermediate product from a tetrazo compound and one molecule of an axe dyestuli' component.

The new coloring matters dye wool from an acid bath in orange-red to blue to black shades fast to lightii to milling and to washing. The dyestu s of this grou as far as they possess the property of orming lakes after treatment with chromates chan e into bluer tints remarkable for their excel ent fastness to milling and washin They are after being dried and pulverized generally from red ish to black powders soluble in water and in concentrated sulfuric acid generally with a reddish to brownishblaek coloration. They yield upon reduction with zinc )owder and acetic acid an amino 2 naphtliol-(i-sulfonic acid compound substituted in the eulfonic group by Application filed February 25, 1814. Serial No. 820,883.

acid having most probably the following general formula:

Rineaning an organic radical which does not further couple in these combinations with a diazo compound, such as of ammonia (NH phenol (OC,,H cresol (OC H,CH,), amin (NHCH,), naphthol (OC, H anilin (NHC H a residue of an amin or a phenol which is free from diazotizable amino groups.

In order to illustrate the new process more fully the following examples are given, the parts being by Weight:

Example 1: 300 partsof2-naphthol-6-sulfonyl-phenyl-ether It forms after bein dried a yellowish-red powder and dyesavoo in pure orange shades very fast to milling.

In quite an analogous manner the condensation products with the homologues of the phenolether or with the naphtholethers, and the sulfonic acids and substitution products of these compounds may be used. Instead of the diazo compound mentioned in the example, any other diazo body may be employed.

Example 2:

299 parts of 2-naphthol-6-sulfanilid:

-OCEh Vo M) After being dried and crushed it forms a It is after being dried and pulverized in the shape of its sodium salt a reddish powder soluble in water and in concentrated sulfuric acid with a reddish coloration. Upon reduction with zinc powder and acetic acid it yields 1-naphthylamint-sulfonie acid and l-amino 2-naphthol-(S-sulfonylsalicylamid.

Similar dyestuffs of the same 00d properties can be obtained on using tie condensation products of the Q-naphthol-l-carboxyl-(l-sulfonyl-chlorid with other aminoortho-oxy-carboxylic acids 6. g. the aminocresotinic acids, or with their derivatives flawsbrownish-red powder which yields on wool pure yellowish-red shades very fast to milling and it differs in this respect from the dycstuflf obtained from 2-naphthol-6-sulfonic acid.

Instead of the condensation compound of the Q-naphthol-l-carboxyl-6-sulfonylchlorid with anilin the condensation products with other amins, such as naphthylamins, with the homologues and substitution products of anilin e. g. toluidin, methylanilin, sulfanilic acid, etc. may be used as coupling components; likewise other diazo-compounds, diazoazo compounds tetrazo compounds or intermediate compounds obtainable by the action of one molecule of a tctrazo compound with one molecule of an azo-dycstutl' component.

Example 3: 359 parts of Q-naphthol-G- sulfonyl-salicylamid are dissolved in an excess of sodium carbonate and the diazo com ound prepared from 223 parts of l-napiithylaminl-sulfonic acid is added to this solution while it is being stirred. When the coupling is finished the dyestufi' is salted out and collected on a filter. It yields on wool a red which changes on being aftertreated with acetate of chrome into a bluish-red of excellent fastness to milling. The new dyestutf has in a free state most probably the formula:

COOK

e. g. the 5-sulfonyl-3-amino-6-oxybenzoic acid or the condensation products with other aminophenols for instance with the 4- chloro-2-aminophenol-6-sulfonic acid other diazo compounds, tetrazo compounds etc. may be used.

\Ve claim: 1. The new azodyes which are after hemg dried and pulverized generally from to dish to black powders soluble in water and in concentrated sulfuric acid enerally with a reddish to brownish-blac: coloration; yielding upon reduction with zim powder and acetic acid an amino-Z-naph thol-G-sulfonic acid compound substituted in the sulfonic group by an organic radical which is free from diazotizable amino groups; and dyeing wool from an acid bath generally from orange-red to blue to black which dye is after being dried and pulverized in the sha e of its sodium salt a reddish powder so uble in water and in concentrated sulfuric acid with a reddish coloration; yielding upon reduction with zinc powder and acetic acid l-naphthylaminisulfonic acid and 1-amino-2-naphthol-6- sulfonylsalicylamid' and dyeing wool from an acid bath in re shades fast to millin and to washin which aftertreated wit chromates are c anged into a bluer shade ure shades fast to milling, substantially as escribed.

2. The new azodye having in a free state most probably the ormula: 10

WILHELM NEELMEIER. AUGUST SIGWART.

Witnesses Hans Bntrcmmn, MARTIN Hunznnno.

00p! of this patent my be obtained (or in cent: each, by addrenln: the Commiuioner of rmau,

Washington, D. 0. 

